CN102803411A - Water-based coating compositions and systems with improved sag resistance, and related methods - Google Patents

Abstract

The present invention provides a water-based coating and/or coating system that can be used to form sag resistant wet layers or coatings on a wide range of substrates. The coating system is particularly effective for protecting metal-containing substrates, such as intermodal cargo containers, against corrosion. As an overview, the present invention provides water-based compositions suitable to form primer coats on substrates. Desirably, the primer incorporates a high level of one or more CAS agents for excellent sag resistance while drying in a broad range of relative humidity environments. Alternatively, modifications can be made to control temperature and humidity during spray application and drying as a way to increase sag resistance of the coating.

Description

Have the water base paint compositions that improves sagging resistance and system and associated method

The cross reference of related application

The right of priority of the U.S. Provisional Application sequence number 61/450,481 that the application requires to submit on March 08th, 2011.

Technical field

The present invention relates to be used at base material, particularly on metallic base material, forming the water-based paint system and the method for supercoat.More specifically, the present invention relates to coating composition, method and coating system, said coating system comprises water-based paint compositions.These coatings are usually as primer coating (also being called as undercoat) or as through metallic coating (" DTM "); Wherein water-based paint compositions preferably has one or more clays anti-sagging dose (after this being called " CAS agent ") of enough high filler loading capacities; And/or this coating is coated in the environment of controlled humidity, to promote of the enhancing of gained coating in the performance aspect the sagging resistance.

Background technology

Through freight freight container (also being called as shipping or shipping container) is reusable transportation and the storage unit that is used between two zones (comprising two countries), carrying product and raw material.The through freight freight container by stdn so that intermodal transportation, such as the intermodal transportation between sea transport, cargo train transportation and the automobile carrier transportation.The stdn of freight container also is called as containerzation.

Containerzation provides many benefits for global commerce.Shipment (shipped goods) carrying can be more easily, more cheap.The goods that loads at the three unities is known by manufacturers can be in the point of destination by unloading easily.Because freight container is usually by sealing and can lock and distort and steal preventing, so improved the security of goods.Freight container also has longer work-ing life, and has bigger market with freight container.In addition, manufacturers since know potential customers are all arranged all over the world and can greater amount ground make freight container, so the cost of itself has reduced.

Some international standards had been founded already to promote trans-containerization.For example, International Organization for Standardization has been issued standard applicatory, comprises the R-668 that defines term, size and grade; The R-790 of definition sign; Recommend the R-1161 of cabinet corner fitting; The R-1897 of the size of setting general-purpose freight container.Other standards comprise ASTM D5728-00; ISO 9897 (1997); ISO 14829 (2002); ISO 17363 (2007); ISO/PAS 17712 (2006); ISO 18185 (2007); With ISO/TS 10891 (2009).IICL (Institute of International Container Lessors (Institute of International Container Lessors)) has stipulated the international norm for paint/lacquer material performance.Also see also International Organization for Standardization, Freight Container (freight container), ISO Standards Handbook, the 4th edition, 2006, the 34th volume of ISBN 92-67-10426-8; And Levinson, Marc, The Box:How the Shipping Container Made the World Smaller and the World Economy Bigger; Princeton, NJ, Princeton University Press; 2006, ISBN 0691123241.These standards and publication are all added among this paper in full, are used for various purposes.

Freight container is at their the harsh corrosive atmosphere of length of life experience.When at sea transporting, freight container is exposed to the brinish corrosive nature.When being exposed to physical environment, freight container must be through wind-engaging, daylight, hail, rainwater, sand and dust, heat etc.The freight container that is exposed to daylight possibly be baked to 82 ℃ (180 ℉) or even higher temperature.

Therefore, freight container must be manufactured into and allow this freight container reasonably holding out against such exposure work-ing life in the duration.As a kind of strategy, freight container can be processed by corrosion resistant material such as stainless steel, weathering steel (COR-TEN board steel or CORTEN board steel).Even the corrosion resistant material by such is processed, usually still hope on freight container, further to apply the further protection of competent, attrition resistant, corrosion-resistant coating as the antagonism deterioration.Also can start from decoration, information or brand identity reason and use coating.

Typical coating strategy is included in and applies top coat on the primer coating.Usually, coating is coated on one or more vertical surface.In history, mainly be that the solvent-based coating system is used to protect freight container, because many aqueous based systems that is suggested can not satisfy suitable performance requriements and/or standard.Particularly; Aqueous coating is difficult in the condition of high humidity amplitude variationization, apply; This is because the coat film of coating keeps moistening and/or can uniform drying in the longer time period, thereby if causes viscosity can't in dry epoch, recover the sagging increase of coating so.Therefore, have only the solvent-based coating system in industry, to obtain the broad commercial acceptance degree.There is very strong prejudice in container industry to using the water-based paint system.

Along with the increase of Environmental awareness, hope very much the improved technology of exploitation, thereby allow to use the water-based paint system to protect freight container or other base materials (for example vehicle, such as railcar or truck).

Summary of the invention

The invention provides a kind of water base paint compositions and/or system; It can be used for forming such coating, and this coating preferably has sagging resistance (for example this coating preferably has sagging resistance in normal and/or moist dry environment) when said composition is dry in various humidity environments.This coating system is effective especially for protection metallic base material (such as the through freight freight container) protect it from corrosion.

Generally speaking, the invention provides aqueous composition, it is suitable on base material, forming primer coating (or DTM coating), and topcoat compositions is provided, and it is suitable for directly or indirectly forming top coat on the coating below.Undesirably, mixed the CAS agent of one or more capacities in the aqueous composition, thereby prevented that this coating from avoiding excessive sag at compsn when (promptly in wet environment and/or in the environment at relatively dry) is dry in various humidity environments.

This discovery has solved to hinder introduces the challenge that water-based paint is used to load and transport freight container market.That is, think in the past to be formulated in the various humidity environments and on lower floor's container surface, show the unusual difficulty of water-based paint system that to accept sagging resistance when dry.Many traditional aqueous based systems, especially containing those systems of chlorinated resin (such as PVDC) can't be in various humidity environments (for example; At confined area and/or owing to season for example, geographical position, these combination and the like have in the external region of high humidity, and/or in the environment of relatively dry) sagging resistance test through being suitable for.For example, when when lower floor's base material acts on just on the exsiccant film with vertical mode setting and gravity always, coming the dry wet coated membrane, these coatings are exceedingly sagging.Therefore, be starved of the sagging resistance that improves these coatings, and increase their available action scope (promptly can be in moist relatively environment and in the environment of relatively dry dry and do not have sagging).Expect very much a kind of commercial water-based paint system that gets that can satisfy the harsh requirement of through freight container industry in the industry.

In one embodiment, the invention provides a kind of aqueous composition, said composition can be used for forming have the excellent anti droop coating such as primer coating.Can have one or more CAS agent (for example 1.5 of the convention amount level to 5 times) of unusual high filler loading capacity according to water-based paint compositions of the present invention, thereby when coating is dry in moist relatively environment, help this coating more anti-sagging.Advantageously, selected CAS agent can't desirably not influence the viscosity and/or the time of drying of coating composition, and/or their anti-sagging function can be exceedingly not impaired.Surprisingly, one or more CAS agent that in preferably water based coating composition of the present invention, comprise elevated levels can desirably influence viscosity, time of drying and/or anti-sagging function in wide range of humidity (for example 45 to 95%) and/or pH (the for example pH of 5-8).

Unfortunately, under the situation of aqueous composition, regulating polytype anti-sagging dose of type and consumption with thickening material maybe be challenging, because one or more physics and/or rheological parameter (for example time of drying and/or viscosity) possibly receive excessive influence.And if the pH of waterborne compositions changes (for example having more acidity along with the coating drying becomes) from any reason, so anti-sagging function possibly receive the influence of not expecting.

As an example; If it is excessive that the viscosity of water-based paint compositions increases; Apply possibly become very difficulty and/or of said composition with practical way so because full-bodied liquid often suppresses to cause coating exsiccant water to discharge, so possibly desirably not increase time of drying.And; If for example pH descends excessive (such as discharging under the situation of ammonia in drying process in coating); So acid coating composition is the base material below the etching exceedingly, and/or the anti-sagging function of selected anti-sagging dose or thickening material possibly receive over-drastic and damages owing to the variation of pH.For example, along with coating composition is dry, pH changes and possibly in the such water-based paint compositions that contains tart chlorinated resin (such as polyvinylidene chloride), take place.

The level of CAS agent is increased to above the conventional level that is used for moist dry environment owing to some reasons possibly be counterintuitive.For example, general knowledge thinks that viscosity will increase to such level when using excessive CAS agent, and under this levels of viscosity, the release of water from compsn possibly suppressed, thereby will desirably not increase time of drying.As another example; It is counterintuitive being increased to the level of CAS agent above conventional levels (for example being higher than 1 pound the per 100 pounds water-based paint compositions (water-based paint compositions of the every 100L of CAS agent of 0.12kg) of CAS agent); This be because hydrophilic clay-based material be moisture absorption and they possibly suppress the release of water from compsn further; Thereby exceedingly increase time of drying.

Surprisingly, the level of CAS agent is increased to above conventional levels can be suppressed at excessive sag in the wet environment, however still allow water from coating, to discharge and can excessive influence time of drying.

Except utilizing particular agent or thickening material control sagging resistance; If be used to apply the measure that comprises controlling moisture with the system of dried/cured coating, so also can utilize the thickening material of other types or the sagging resistance that rheological agent improves paint base composition.The humidity condition of baking oven during the dried/cured of the humidity condition of (spray booth) and coating between spraying during through the control applying coating allows the wet film of coating dry equably as follows: to eliminate and sagging (being that shear action is on the wet film that is coated on the base material of vertical placement) the relevant problem that is caused by high humidity environment.

Embodiment

Embodiment of the present invention as described below is not to be intended to exhaustively, or the present invention is restricted to disclosed precise forms in the following detailed description.Or rather, selecting and describe these embodiments is can be familiar with and understand principle of the present invention and enforcement for others skilled in the art.All patents that this paper quoted, patented claim in a review, disclosed patented claim and technical article insert this paper respectively by reference in full, are used for all purposes.

Water-based paint compositions of the present invention is used in and forms primer coating (or " DTM " coating) on the base material.In some embodiments, water-based paint compositions can be as first waterborne compositions in the coating system of the present invention.In order to simplify purpose, but also unrestricted, water-based paint compositions of the present invention will be described to first waterborne compositions in the coating system of the present invention as follows in detailed description.

In one embodiment, coating system of the present invention comprises first water-based paint compositions usually and preferably, and this coating composition can be used on base material, form corrosion resistant primer coating (or DTM coating).At first aqueous coating during as priming paint, this system preference and optional second water-based paint compositions that further comprises, this second water-based paint compositions can form competent, attrition resistant top coat on first/primer coating.Submit simultaneously in the applicant's application therewith, autograph has been for having described relevant coating system in the common co-pending application of " WATER-BASED COATING SYSTEM WITH IMPROVED MOISTURE AND HEAT RESISTANCE ".

In one embodiment, first water-based paint compositions comprises following composition usually and preferably, and said composition comprises with aqueous carrier blended first resin Composition at least and is dispersed in one or more CAS agent in the said water-based paint compositions.First water-based paint compositions of the present invention can be a single phase soln, wherein, comprises that at least one or more compositions of said first resin Composition are dispersed in the said aqueous carrier basically fully.Perhaps, said coating composition can comprise two phases or more heterogeneous.Contain two mutually or more the heterogenetic compsn can be the dispersion-s form, such as wherein one mutually or the dispersion-s in the heterogeneous external phase that is dispersed in another material and/or another phase.Some dispersion-ss are suspensoid forms, include but not limited to the colloidal suspensoid.In some embodiments, coating composition is wherein to include latex or the emulsion form that is dispersed in the polymer particles in the aqueous carrier.When using in this article, " latex " polymkeric substance means, and polymkeric substance mixes with aqueous carrier under the assistance of at least a emulsifying agent (for example tensio-active agent), thereby is formed on the emulsion of the polymer beads in this supporting agent.

In some embodiments, compsn as herein described can be water dilutable, this means, if said composition is stable with the water-reducible words maintenance of additional quantity.For the water-dilutable compsn, some embodiments use and at least aly can under the situation that need not use independent tensio-active agent, be dispersed in the polymkeric substance in the water, but can use independent tensio-active agent if desired.Under the situation that does not need independent tensio-active agent, just can be dispersed in polymkeric substance in the water and comprise the ionic functional group and/or the hydrophilic segment of suspension usually, they make the respective regions of this polymkeric substance more compatible with water.Possibly need external acids or bases for negatively charged ion is stable, but such acids is different with the emulsifying agent that is used to disperse latex polymer (for example tensio-active agent) usually with bases.

In one embodiment, first resin Composition comprises at least a film-forming resin, and this film-forming resin desirably assists top top coat to adhere to better on the following base material, and/or be combined as base material with this top coat extra protection is provided.Those be intended to be used in be coated with or not by the embodiment on the matel coated base material in; Resin in said first resin Composition desirably forms such coating; Enough waterproof steam of this coating or liquid; And desirably be hydrophobic, thereby help reduce oxidation or other deteriorations that possibly cause by moisture.

The resin that can be used in first resin Composition can be heat cured and/or thermoplastic.Expediently, one or more in these are thermoplastic.In addition, some embodiments that can be used on the thermoplastic resin in the present invention practice can be unbodied, crystalline or hemicrystalline.That the exemplary resin that is used for first resin Composition comprises is acyclic, cyclic, resin branching, linear, aliphatic series or aromatics.Thermoplastic resin preferably have be lower than 65 ℃, preferably be lower than 45 ℃, more preferably less than 25 ℃ minimum film-forming temperatures (MFFT).Hope that also this resin preferably has and is higher than-50 ℃, preferably is higher than-25 ℃, more preferably is higher than 0 ℃ minimum film-forming temperature.

The molecular weight of one or more resins in first resin Composition can change in wide region independently of one another.If molecular weight is low excessively, coating maybe be durable inadequately or can not resists solvent and attack so.If too high, this coating is not easy to apply under enough level of solids so.Weigh the advantages and disadvantages, number-average molecular weight is preferably in about scope of 5000 to 75,000, more preferably in about scope of 10,000 to 50,000, more preferably in about scope of 10,000 to 20,000; Weight-average molecular weight is preferably in about scope of 8,000 to 150,000, more preferably in about scope of 20,000 to 80,000, more preferably in about scope of 35,000 to 55,000.Only if statement is arranged in addition, the molecular weight that this paper uses is meant number-average molecular weight (Mn).

Preferably, first resin Composition comprises at least a chlorinated resin of being derived and being obtained by one or more reactants, and at least a part at least in the wherein said reactant is by chlorination.Chlorinated resin helps to provide the coating with excellent anticorrosive, in ocean environment, has the coating of excellent anticorrosive especially, wherein in ocean environment, receives the base material of coating system protection to be exposed to solvent, fresh water, salt solution etc.Cl substituting group in the chlorination reaction thing can or be directly connected on the skeleton of reactant via suitable link group through singly-bound.In some embodiments, the chlorination reaction thing can be monomeric form, oligopolymer form and/or polymer form.The functionality that can have in some embodiments, free redical polymerization.

Except one or more chlorination reaction thing, can also use one or more extra copolymerisable monomers, oligopolymer and/or resin with chlorinated resin if desired.The chlorination reaction thing preferably accounts at least 50 weight % of gained chlorinated resin, more preferably at least 70 weight %, even more preferably at least 85 weight %, even up to 100 weight %.

Cl content in the gained chlorinated resin can change in wide region.Therefore, the resin embodiment can be by the part chlorination or by perchlorizing.If Cl content is low excessively, the erosion resistance that is provided by this resin so possibly be lower than desirable.Cl content can be characterized as being, the weight percent of the Cl that chlorinated resin comprised.For the corrosion protection of higher level, hope that chlorinated resin comprises the Cl at least about 20 weight %, preferably at least about the Cl of 40 weight %, more preferably at least about the Cl of 60 weight %.The perchlorizing embodiment is represented the actual upper bound of Cl content.

The chlorinated resin of type described herein can be by the incompatible preparation of the radical polymerization of chlorinated monomer.Chlorinated monomer preferably includes for example have the free redical polymerization functionality reactant of (for example carbon-carbon double bond), and has and contain preferred 2 to 20, more preferably 2 to 10, the structure of 2 to 4 carbon atoms and at least one carbon-carbon double bond most preferably.More preferably ethylene chloride, propylene dichloride and these combination is such as monochloro ethene, vinylidene chloride, 1,2-dichloroethene, 1; 1,2-trieline, zellon, 1-propenyl chloride, 2-propenyl chloride, 1,1-dichloropropylene, 2,2-dichloropropylene, 1; 2-dichloropropylene, 1,1,1-three chloro-2-propylene, 1,1; 2-three chloro-1-propylene, 1,2,3-tri chloropropene, these combination, or the like.

The chlorinated resin of type described herein can also be by the monomer of the acid anhydrides of chlorinated monomer and ethylenic unsaturated ester class, amides and carboxylic acid or the incompatible preparation of radical polymerization of comonomer.Suitable olefinic unsaturated comonomer for example comprises; (methyl) vinylformic acid and verivate are such as (methyl) glycidyl acrylate, methylacrylic acid, (methyl) vinylformic acid methylamino ethyl ester, (methyl) vinylformic acid tertiary butyl amino ethyl ester, (methyl) acrylic amide, 4-penta guanamines (4-pentanoguanamine), hydroxyalkyl acrylate (such as (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate), (methyl) vinyl cyanide, N-alkoxyalkyl acid amides (such as methoxymethyl (methyl) acrylic amide and butoxy-(methyl) acrylic amide), hydroxyalkyl amide (such as N-methylol (methyl) acrylic amide); Dicarboxylicacid is such as toxilic acid; These corresponding acid anhydrides (if any); These combination or the like.

Preferred chlorinated resin can be according to USP 4,341,679; 4,401,788,4,435,478; 4,543,386 and 4,783, preparation described in 499.

Except having one or more Cl substituting groups and free redical polymerization functionality, the chlorination reaction thing that is used to prepare chlorinated resin can be replaced or not by its replacement by the functionality of extra kind (comprising for example epoxy functionalities) in addition.Such functionality can be selected to crosslinked.As additional option, such functionality can be used for for resin whole dispersing functional degree being provided.The certain substituted base can be the common ring members (co-member) of ring structure.Other substituent instances comprise the combination of hydroxyl, sulfydryl, amino, carboxamido-group, NCO, cyanic acid, carboxylic acid group, sulfate group, sulfurous acid ester group, fatty acid-based, epoxy group(ing) and these groups.

Compsn can also comprise the radical addition polymerization thing of one or more other types; For example in one or more following monomeric water-based emulsions, process through radical addition polymerization or multipolymer; Said monomer is such as for having (methyl) alkoxyalkyl acrylate, vinylbenzene, (methyl) vinyl cyanide, allyl group oxygen class, cyanate, vinyl-acetic ester, vinyl ethers, vinylchlorid, ethene, the cis and trans 1 of 1 to 12 carbon atom in (methyl) alkyl acrylate of having 1 to 12 carbon atom in the vinylidene chloride, alkyl, the alkyl; 3-divinyl, cis and trans isoprene, cis and trans chlorine pentadiene, 1-decene, 1-amylene and 1-octene, these combination or the like.

The free redical polymerization functionality is expediently through following reaction: in the presence of the reagent of assisting to promote required reaction (for example initiator etc.), reactant is exposed to suitable curing energy source usually.Be used for realizing that the polymerization of curable functionality and/or crosslinked energy source can be actinic (radiation that for example has the wavelength of spectrographic ultraviolet or visibility region), accelerated particle (for example electron beam irradiation), thermal source (for example heating or ir radiation), or the like.

Preferred especially chlorinated resin is polyvinylidene chloride (PVDC).The polyvinylidene chloride that this paper uses is meant such resin, and wherein vinylidene chloride occupies at least 40 weight % of the reactant of making this resin; Optional at least 60 weight %; Also optional at least about 75 weight %, also optional, also optional even up to 100 weight % at least about 90 weight %.The embodiment of the suitable polyvinylidene chloride resin of wide region can derive from commercial source.The instance of the commercial embodiment that can get comprises; But be not limited to; With trade(brand)name DIOFAN (can derive from Dow Chemical and/or Solvay Plastics), POLIDENE (for example 33-082,33-038,33-086,33-083,33-075 and 33-081; Can derive from Scott Bader), HALOFLEX (for example 202 and 202S, can derive from DSM Neoresins), PERMAX (for example 803 and 805, can derive from Lubrizol) can get those, these combination or the like.On the one hand, PVDC or other commerce chlorinated resin that can get can be used specific functional group (such as epoxy-functional) modification.

In an embodiment of the invention, thus water-based PVDC compsn handled to improve its pH make said composition acidity less (for example making it have the pH in 3 to 8 scopes).Submit simultaneously in the applicant's application therewith, autograph has been for having described the mode of regulating pH in the common co-pending application of " WATER-BASED COATING SYSTEM WITH IMPROVED MOISTURE AND HEAT RESISTANCE "; The full content of this patented claim inserts this paper by reference, is used for various purposes.

First resin Composition preferably comprises at least about 50 weight %, more preferably from about 50 to 70 weight %, the chlorinated resin of 75 to 100 weight % most preferably from about, such as PVDC.

Except chlorinated resin, the optional resin Composition that comprises one or more other kinds of first water-based paint compositions.Preferably, these components are hydrophobic and basically can be miscible with chlorinated resin, thereby have avoided being separated of any not desired amount between the resin basically.Exemplary resin comprises epoxy resin, urethane resin, polyamide resin, polyimide resin, halogenated polymer, silicone resin, vibrin, Synolac, polyolefin resin, (methyl) acrylics, these combination or the like.The acrylic latex emulsion is preferred, comprises the for example Synolac dispersion-s of polyurethane dispersions (PUD), pure acrylic acid class emulsion, styrene-propene acids emulsion, acrylic-modified.On the one hand, styrene-propene acids emulsion is preferred.The amount of these resins can be selected in wide region, depends on the pros and cons balance of consistency and coating performance (with regard to erosion resistance and thermotolerance).Preferably; First water-based paint compositions comprises; Based on the gross weight of the resin Composition in first water-based paint compositions, about at the most 50wt%, preferred about acrylic latex emulsion of 5 to 50wt%, more preferably from about 15 to 40wt%, most preferably from about 20 to 30wt%.

The amount of first resin Composition in first water-based paint compositions can be selected in wide region.Generally speaking, if the amount of resin Composition is low excessively, possibly be difficult to film forming so, more be difficult to formation base material is had enough adhering film, this film possibly have insufficient erosion resistance or other performances, or the like.If use too high amount, possibly more be difficult to prepare so and add pigments system or more be difficult to process the material that can be coated on the base material.Weigh the advantages and disadvantages, first water-based paint compositions preferably comprises, based on the gross weight of water-based paint compositions, and about 10 to 70 weight %, more preferably from about 15 to 50 weight %, said first resin Composition of 20 to 40 weight % most preferably from about.

First resin Composition is and the aqueous carrier blended." water-based " used among this paper be meant, based on the gross weight of said supporting agent, at least about 5 weight %, preferably at least about 20 weight %, more preferably at least about 40 weight % even be water more preferably at least about 60 weight % even 90 weight % or more supporting agent.Most preferably, about 85 to about 100 weight %, more preferably from about 95 to about 99 weight % is water.

Except water, also optional one or more the extra optional supporting agents altogether that comprises of the aqueous carrier of first water-based paint compositions.(comprise and assist film forming and/or paint vehicle to stablize) for various purposes, can use common supporting agent.Suitably the instance of supporting agent comprises altogether, and (for example ester is pure, like Eastman Texanol product for ethylene glycol butyl ether (butyl cellosolve), alcohols (such as butanols), coalescing agent; And/or low VOC coalescing agent; Like USP 6,762,230 and 7; Described in 812,079), glycol ethers, these combination or the like.Desirably, the so-called common supporting agent (VOC-exempt co-carrier) that does not contain VOC is preferred.

The amount that is included in the common supporting agent in first water-based paint compositions can change in wide region.Consumption depends on various factors, comprise common supporting agent type, add supporting agent altogether purpose, possibly be used for first water-based paint compositions is coated to coating technique on the base material or the like.In the exemplary embodiment; First water-based paint compositions can comprise; Based on the common supporting agent and the gross weight of water that are included in the said composition, about 0.3 weight % is to about 80 weight %, preferred about 0.3 weight % to 15 weight %, the 1 common supporting agent to about 5 weight % more preferably from about.

Except first resin Composition with the aqueous carrier, first water-based paint compositions preferably comprises one or more CAS agent of capacity so that sagging resistance to be provided." CAS agent " that this paper uses is meant such clay material or clay-based material, and this clay material or clay-based material can be comprised in the water-based paint compositions of the present invention with the amount that is enough to make water-based paint compositions when being coated to after drying on the vertical base material with form membrane, to have the resistance to flow of required degree (not can excessive sag).For example, the CAS agent that this paper uses is meant such material, and it can help water-based paint compositions of the present invention to satisfy described in an embodiment as follows wet method sagging resistance test (Wet Sag Resistant Test).The CAS agent can comprise have layered crystal structure silicate minerals as main ingredient (at least 50 weight %).The example comprises, terre verte, bentonite, polynite, saponite, hectorite or the like.A kind of preferred clay material comprises bentonite.These clay materials can use separately or with its two kinds or more kinds of form of mixtures uses, they are normally hydrophilic and moisture absorption.

The applicant finds; Unusual high-caliber CAS agent can prevent that water-based paint compositions from avoiding when dry in moist relatively environment sagging, however not excessive influence viscosity and/or not excessive influence time of drying and/or excessively do not receive the influence of coating composition pH.It is counterintuitive that the level of CAS agent is increased to above conventional levels, because known CAS agent meeting increases viscosity and can moisture absorption.And observations has highlighted the effect of CAS agent in wet environment and has done, the level that increases non-clay base thickening material (for example associative thickener) can not improved the sagging resistance in certain moist scope.Note that in first water-based paint compositions according to the present invention, comprising one or more CAS agent can provide suitable sagging resistance in wet environment and in the environment at relatively dry.

One or more CAS agent can be can prevent that waterborne compositions from avoiding sagging amount and existing when the coating on the vertical base material is dry under different moisture levels environment and condition.In some embodiments, dry environment have in 50 to 99% relative humidity scopes, more common humidity in 50 to 90% relative humidity scopes." relative humidity " that this paper uses can be expressed as, the ratio of the saturation steam dividing potential drop of the vapor partial pressure of air and the air under actual dry-bulb temperature.Relative humidity through dividing potential drop obtains is represented as follows:

wherein,

P _W=vapor partial pressure

P _WS=the saturation steam dividing potential drop of air under actual dry-bulb temperature

Can be used on CAS agent of the present invention can be naturally occurring or synthetic, and can perhaps can be modified, such as the clay that is modified." clay that is modified " that uses among this paper is meant the reformed clay of its surface chemistry property.The clay mineral that is modified is known, and the example is disclosed in U.S. Patent number 7,109, in 257 (people such as Lorah) and the U.S. Patent Publication 2009/0098169 (people such as Ootake).The clay that preferably is modified comprises by organically-modified clay.Also can be called as " organic clay " by organically-modified clay." by the organically-modified clay " or " organic clay " that use among this paper refer to, by clay mineral, the cation-modified clay that obtains through deriving as follows of the clay mineral of terre verte class (for example bentonite, polynite, hectorite, saponite or the like) usually: be present in the inorganic exchangeable cation (being generally alkali metal cation or alkaline earth metal cation) in the natural clay mineral with containing at least one organic cation with alkyl of enough carbon atoms (for example quaternary ammonium alkyl ion) replacement separately.The have various surface wetting characteristics organic clay of (for example hydrophobicity or wetting ability) has been described in the document.The wetting ability organic clay for example utilizes usually, and the IX of the substituted quaternary ammonium compound of polyethers prepares.These organic claies can be dispersed in the aqueous based systems, and can be used for such as the rheology control in the product of latex paint.Preferred organic clay comprises by the bentonite of quaternary amine modification.By organically-modified clay is known, and the example is described in U.S. Patent number 4,743, in 305 (people such as Doidge).

Various CAS agent used in this invention is commercially available.For example; Be applicable to CAS agent of the present invention can trade(brand)name BENTONE

LT from Elementis Specialties; Inc.; Hightstown, NJ is purchased.BENTONE

LT is a wetting ability organoclay materials product, and it is the combination of Natvosol and bentonite clay.

In some embodiments, have found that associative thickener can not play good effect (for example they can excessively increase time of drying) aspect sagging in help suppressing first water-based paint compositions of the present invention in wet environment." associative thickener " that this paper uses is meant any water-soluble polymers with hydrophobic mode modification, and this polymkeric substance can interact with self or with another species in aqueous solution.Hydrophobically modified can strengthen water-soluble polymers make the water thickening or with the ability of other hydrophobicity species and surface interaction.These other hydrophobicity species include, but not limited to the hydrophobic materials of tensio-active agent, the surface of latex particle, the hydrophobic surface of pigment or any other components in the water-based paint compositions.The instance of associative thickener comprises non-ionic ammonia carbamate, polyethers urea urethane, acrylic ester polymer, ether of cellulose, polyoxyethylene glycol and these combination.On the one hand, first water-based paint compositions as herein described is substantially free of associative thickener, wherein " is substantially free of " to be meant, less than the amount of about 5wt% of the gross weight of first water-based paint compositions.

As what mentioned, even CAS agent (for example hydrophilic clay and/or the clay that is modified) preferably exists with unusual high level, the dry basically time that is spent of this first water-based paint compositions can be excessively not influenced yet.Be considered to compsn to time that " surface drying " spent time of drying in the art.In some embodiments, according to first water-based paint compositions of the present invention can under 50 to 90% the relative humidity under 25 ℃ in 10 to 45 minutes time period, preferably under 50 to 90% the relative humidity under 25 ℃ at 15 to 30 minutes time period inner drying.

In order to help to provide according to the suitable sagging resistance under wet environment of the present invention, said one or more CAS agent with the water-based paint compositions of per 100 gallons (every 100L) greater than 1 pound (0.12kg), greater than 1.25 pounds (0.15kg), greater than 1.5 pounds (0.18kg), greater than 2.0 pounds (0.24kg), greater than 2.5 pounds (0.30kg), greater than 3.0 pounds (0.36kg) or even exist greater than the amount of 4.0 pounds (0.48kg).Typical scope comprises the water-based paint compositions of per 100 gallons (every 100L), 1.5 pounds to 15 pounds (0.18 to 1.8kg), 2.0 to 5.0 pounds (0.24 to 0.60kg) or even 2.5 to 4.0 pounds (0.30 to 0.48kg).

In order to help to provide according to the suitable sagging resistance under wet environment of the present invention, said one or more CAS agent have less than 2 microns, the preferred size of particles in 0.05 to 2 micrometer range.Size of particles is meant, the diameter of clay particle (diameter of irregular size is the longest distance between its lip-deep two points).

" sagging resistance " according to first water-based paint compositions of the present invention is meant, the anti-flowability of this first water-based paint compositions.In the description of this paper, sagging resistance is according to sagging resistance thermometrically as described below, but routine is measured with reference to ASTM Method D 4400.In some embodiments, first water-based paint compositions according to the present invention has at least 6 Mills (0.015cm), preferably at least 8 Mills (0.02cm), preferably at least 10 Mills (0.025cm), the anti-sagging value according to the sagging resistance measurements determination of at least 12 Mills (0.03cm) most preferably in the environment of humidity greater than 65% relative humidity.Preferably in the environment of humidity, has the anti-sagging value to the scope of 16 Mills (0.04cm) according to first water-based paint compositions of the present invention according to the sagging resistance measurements determination at 8 Mills (0.02cm) greater than 50% relative humidity.

As mentioned, even the CAS agent exists with unusual high level, the viscosity of this first water-based paint compositions can not receive excessive influence (for example at lay up period) yet.Surprisingly, use the CAS agent can make water-based paint compositions have stable viscosity.As the example of stable viscosity, when under about 25 ℃ of temperature to about 49 ℃ of scopes, storing, viscosity change can surpass+/-20% (preferred+/-10% ,+/-5% or even+/-2%)." Stormer viscosity " is meant that the viscosity measurement in the Stormer viscosity apparatus is in Krebs unit.Stormer viscosity is measured according to ASTM Method D 562.In some embodiments, first water-based paint compositions according to the present invention have under 25 ℃ 50 to 90Krebs unit's scope, preferably 25 ℃ of viscosity in 60-70Krebs unit's scope.

Also as mentioned, what the pH of first water-based paint compositions preferably can excessive influence CAS agent is functional." pH " of water-based paint compositions is the negative logarithm of Sorensen value.In some embodiments, first water-based paint compositions according to the present invention in coating composition at least one section in time of drying, have in 4 to 9 scopes, more preferably in 4.5 to 7.5 scopes, the pH in 5 to 7 scopes most preferably.

Advantageously, in first water-based paint compositions, comprising unusual high-caliber CAS agent can excessive influence preservation period stability (shelf-life stability)." preservation period stability " that this paper uses is meant that the viscosity of water-based paint compositions and/or anti-droop can not change basically under typical time span and temperature for preservation period.In the exemplary embodiment, first water-based paint compositions according to the present invention has at least 4 months, preferred at least 6 months preservation period stability.Preservation period stability can be measured through following; The encloses container of water-based paint compositions was placed in " the hot box " of 120 ℉ (49 ℃) 14 days.Preferably, bonding and/or anti-droop changes after following 14 days and can surpass 20% at 49 ℃, preferably changes being no more than 10%, 5% even 2% after following 14 days at 49 ℃.

Except first resin Composition, aqueous carrier and one or more CAS agent, optional one or more supplementary components that also comprise in first water-based paint compositions.When selecting supplementary component, the minimum selection of risk of the degraded chlorinated resin of sening as an envoy to is done in hope.For example, in some traditional P VDC based coating compositions, generally comprise and contain the Zn composition.These instance comprises zinc, zinc salt and/or zinc oxide.Containing the Zn composition some benefits can be provided like this.These benefits comprise that erosion resistance, protection avoid dodging rust or the like.

Yet such compsn possibly cause the degraded of chlorinated resin, especially under the elevated temperature that is higher than about 140 ℉ (60 ℃).Do not hope to be entangled in theory, it possibly be because the dechlorination hydrogenation that some metal and containing metal species (such as zinc, iron, tin etc.) can the catalytic chlorination resins when this resin is exposed to comparatively high temps that this degraded is considered to.This degraded can reduce the quality of gained coating, and possibly be such as bubble, peel off, problem such as crackle facilitate factor.Other transition metal (such as iron, tin etc.) also possibly have similar catalytic activity, and can cause similar degradation problem.

May reside in some embodiments in first water-based paint compositions at catalytically-active metals or containing metal species (for example Zn or contain the Zn species) etc., use the blended metal can reduce catalytic activity and help stable composition.The stabilization that hybrid metal for example, in the system that comprises barium/zinc combination, calcium/zinc combination, barium/calcium/zinc combination etc., possibly occur.On the one hand, when stablizing through the blended metal system, first water-based paint compositions preferably comprises about 25wt%Zn, more preferably from about 10wt% to 20wt%Zn, most preferably from about 5wt% to 15wt%Zn.

In some embodiments, catalytic metal or some form that contains the catalytic metal species can be passivated or be closed, thereby have suppressed or significantly reduced the catalysis dechlorinationization of the resin that is caused by this metal.Such species can be comprised in first waterborne compositions and can not cause remarkable dechlorination.Suitable species include, but not limited to some Zn salt, comprise the Zn salt of solubility, such as Zn (NO ₃) ₂, ZnSO ₄Deng.On the one hand, in the time of in being present in first water-based paint compositions, contain the Zn species preferably with about 2wt% to about 15wt%, more preferably with about 2wt% extremely about 10wt%, most preferably with about 2wt% extremely about 5wt% exist.

Even have stable possibility, still hope restriction in some embodiments or even from first water-based paint compositions, get rid of the composition that possibly contain the metal (such as zinc) that can have catalytic activity at least basically the degraded of chlorinated resin.In its use, will be exposed to comparatively high temps if estimate the gained coating, it is preferred especially to get rid of such catalytically-active metals so, because these metals are often more active under comparatively high temps.In fact; Observed already, and (comprised from filler, dodge rust inhibitor, pigment and other additives) in the various sources from first water-based paint compositions and get rid of zinc and contain Zn composition and can significantly improve the thermotolerance of PVDC resin material and reduce the gained coating foaming significantly, peel off and rimose trend.Therefore, because some metals (such as Zn) may promote chlorinated resin at high temperature to degrade, has the composition of the catalytically-active metals pollutent of minimum (if any) so possibly hope selection, especially under the stable on heating situation of needs.On the one hand, when hoping thermotolerance, first water-based paint compositions preferably comprises the Zn that is no more than about 10wt%, more preferably no more than the Zn of about 7wt%, is most preferably not exceeding the Zn of about 5wt%.

Consider these and select principle, can in first waterborne compositions, mix one or more supplementary components.For example, for preparing optional one or more HCl scavenging agents that comprises of the employed composition of coating composition of the present invention.The HCl scavenging agent is removed free HCl valuably, thereby suppresses the further degraded of PVDC resin.Preferred HCl scavenging agent comprises epoxy functionalized molecule, dodges rust inhibitor, dienophile, inhibitor, metal chelate compound, isocyanate compound, organosulfur compound or the like, and it is submitted in the applicant's application therewith simultaneously, autograph is to further describe in the common co-pending application of " WATER-BASED COATING SYSTEM WITH IMPROVED MOISTURE AND HEAT RESISTANCE ".

One or more anticorrosive agents be possibly also hope in said compsn, to be mixed with, thereby base material and gained coating protect it from corrosion below the further protection helped.In these some are based on heavy metal, such as Pb or Cr.Other appropriate environments friendly materials comprise barium, calcium, silicophosphate, calcium titanate, Calucium Silicate powder (the for example amorphous silica of calcium ion-exchanged), condensed phosphoric acid calcium (condensed calcium phosphate), aluminium triphosphate or the like.Aluminium triphosphate is preferred.Various this type pigment are commercially available.But a kind of commercial examples can be obtained by Grace Davison by trade(brand)name SHEILDEX AC-5.

When the needs thermotolerance, the mode of should be left out with the catalytically-active metals of the significant quantity that helps to cause the chlorinated resin degraded (or otherwise passivation) is selected optional anticorrosive agent.For example, the common and zinc oxide blend of some commercially available aluminium triphosphate materials, and other aluminium triphosphate materials are substantially free of zinc usually.Can not meet the application of relatively-high temperature during use for the gained coating, it possibly be acceptable using the aluminium triphosphate of blend.Yet,, possibly preferably use the aluminium triphosphate that is substantially free of catalytically-active metals (such as Zn) so if this coating possibly meet with high temperature.

The amount of used anticorrosive agent can change in wide region.If use very little, corrosion protection property maybe be less than desirable so.Use too much maybe not can to provide with using and compare significant Additional Protection more on a small quantity.Weigh the advantages and disadvantages, use coating solid about 1 to about 20 weight parts, more preferably this reagent of 2 to 15 weight parts will suit with respect to 100 weight parts.In an illustrative embodiments, use will suit with respect to the no zinc aluminium triphosphate of about 5 weight parts of coating solid of 100 weight parts.

Hope comprises one or more fillers, extender or the pigment (after this being called " filler ") of q.s in first water-based paint compositions, thereby further improves corrosion protection and/or in case be coated in the perviousness of passing through coating that provides best on the metal base.In addition, filler can be used as thickening material, thereby helps to reduce the sagging resistance that foams and help to improve coating composition.

Be not to be entangled in theory, the special properties of filler (comprising oil absorbency, particle shape, particle size, length-to-diameter ratio, porosity, surface treatment, ionic effect etc.) is considered to have the erosion resistance of the coating of helping.Tensio-active agent in first coating composition and resin concentration also possibly influence the selection of suitable filler or filler mixture.

The filler that is applicable to first water-based paint compositions comprises; One or more insoluble compound among Be, Mg, Ca, Sr, Ba, Al, Ti, transition metal, lanthanide series metal, actinide metals, Si, Ge, Ga, Sn, the Pb, these combination or mixture or the like.Insoluble compound comprises vitriol, oxyhydroxide, carbide, nitride, oxide compound, oxynitride, oxycarbide, silicate and/or carbonate.The embodiment of filler comprises talcum, CaCO like this ₃, BaSO ₄, pure aluminium silicate, white lake, mica, silica (with for example granulated glass sphere form), wollastonite, china clay, chlorite, rhombspar, above-mentioned mixture or combination, or the like.BaSO ₄, CaCO ₃, rhombspar and wollastonite be preferred.On the one hand, first water-based paint compositions comprises the mixture of two kinds or more kinds of fillers.

On the one hand, the filler that is used for first water-based paint compositions comprises non-sheet shape (for example nodositas, needle-like, sphere) particle and sheet shape (for example flats, laminar) particle.Have sheet shape particulate exemplary pigments and include but not limited to mica, talcum, chlorite, its mixture or the like.Having non-sheet shape particulate exemplary pigments includes but not limited to; Insoluble vitriol, carbide, nitride, oxynitride, oxycarbide, oxide compound and/or the carbonate of Be, Mg, Ca, Sr, Ba, Al, Ti, transition metal, lanthanide series metal, actinide metals, Si, Ge, Ga, Al, Sn, Pb, its combination or the like.

In one embodiment, select suitable filler based on oil absorbency.One preferred aspect in; First water-based paint compositions comprises the combination of suitable filler or two kinds or more kinds of fillers, and said filler is measured to have according to ASTM D281 (standard method of test of the pigment oil absorbency of wiping through spatula) and is not more than per 100 gross weights of about 50g oil, preferred about 5 to 40g/100g, more preferably from about 10 to 30g/100g, 15 to 20g/100g oil absorbency most preferably from about.

In one embodiment, select suitable filler based on the length-to-diameter ratio of filler.Be not to be entangled in theory, lower length-to-diameter ratio is considered to provide excellent corrosion protection property and to the adhesivity of metal base.Be not to be entangled in theory, the length-to-diameter ratio of specific fillers has the oil absorbency that helps filler, and the filler that promptly has low length-to-diameter ratio can show lower oil absorbency.Oil absorbency can also receive particle size and/or can influence the influence of arbitrary parameter of the surface-area of filler particles.

On the one hand, have non-sheet shape particulate filler can with have sheet shape particulate filler combination and use.The weight ratio of non-sheet shape and sheet shape pigment can change in wide region.In the exemplary embodiment, this ratio can be in about 1: 50 to 50: 1 scope, preferably in about 1: 10 to 10: 1 scope, more preferably in about 1: 3 to 3: 1 scope, change.For example, an embodiment of first water-based paint compositions comprises, coating based solid gross weight, the circular relatively BaSO of about 14.5 weight % ₄The sheet shape mica particles of particle and about 14.5 weight %.

In one embodiment; First waterborne compositions comprises the filler particles of q.s; The coating that the result is processed by this first coating composition comprises; Based on the TV of dry coating, about 1 to 40 volume %, preferred about 5 to 30 volume %, the pigment of 10 to 25 volume % (being filler) volumetric concentration (PVC) more preferably from about.Be not to be entangled in theory, pigment volume concentration (PVC) is considered to playing an important role aspect the erosion resistance of first water-based paint compositions.Under the pigment volume concentration (PVC) of the best, filler particles can change the surface energy of first water-based paint compositions with the mode of steam breathability, surfactant migration and the erosion resistance of the first coating composition film that on base material, forms of influence.

Can use various technology to prepare first water-based paint compositions by required composition.According to exemplary techniques, keep first resin Composition, meanwhile make up and mix other compositions up to evenly.Then, first resin that keeps added in the mixture further mix, up to evenly.

According to another technology, first water-based paint compositions can be through being prepared as follows: one or more CAS agent are dispersed in the aqueous carrier under the condition that can make these one or more CAS agent form aqueous dispersion and can excessively not reunite.Preferably, the ammonia that can add capacity is assisted the dispersion of CAS agent, makes that this reagent can building network and suitable sagging resistance is provided in wet environment.After processing aqueous dispersion, can aqueous dispersion be mixed with resin Composition then, thereby form water-based paint compositions.

In some embodiments, for the sagging resistance that helps in wet environment, to provide suitable, can to coating composition apply therein and between solidified spraying on the substrate surface and/or the cure/dry baking oven make amendment.On the one hand, between this spraying and/or the baking oven system be modified to and comprise that air is removed and exchange system.Be used for baking oven system that drying coated is layed onto five coatings on the freight container and description arranged in for the common pending trial U. S. application of " SYSTEM AND METHOD FOR DRYING FIVE-SIDED CONTAINERS " number 12/837,833 at the applicant's, autograph that submit on July 16th, 2010.

The air displacement system is with the air of discharging outside air displacement fresh, heating is between industry and commercial building or spraying; (thereby with heating or other modes) keep constant air outlet temperature (leaving-air temperature), no matter and AT that gets into and outside air temperature how.For every cubic feet of air of between spraying or the baking oven, discharging or remove, the air displacement system replenishes the fresh air of equivalent.

Usually, the exhaust system between spraying removes the air of significant quantity during operation.Typical 10 ' * 8 ' * 6 ' (3.05m * 2.4m * 1.8m) can discharge above 8000 cubic feet of (226.5m by PM between spraying ³) air.If directly introduce displaced air from the outside, this volumes possibly enough cooled off the inside of building and will influence the quality of coating unfriendly so.Air displacement system (comprising the air displacement unit) for the spraying between provide regulated, the mistake filterable air, thereby make variation of temperature minimum.Such air displacement system also preferably removes any PM for particulate matter that possibly cause disadvantageous effect to the final quality of coating.

Under the situation between the pressurization spraying, in air displacement is introduced directly between spraying, thereby eliminated the demand that sucks air from the outside.This allow to control better in the environment between spraying temperature with filter quality, thereby significantly improved the coating quality, and eliminated and sagging relevant problem in wet environment or in having the environment of variable temp.

On the one hand, the air displacement system is designed to have variable speed drive/motor and air door equipment (damper package), thereby the air of discharging 140 ℉ (60 ℃) or 160 ℉ (71 ℃) solidifies or dry recycle with acceleration.This design reduces 50% with airflow of drying stage, and utilizes the constant displacement of the damp atmosphere that extraneous air forms in baking oven because aqueous coating system of the present invention is dry to guarantee.

Air displacement as herein described system also comprises automatic-balancing system with variable frequency driver airflow with automatic adjusting vent fan, thus during applying between spraying and in baking oven during the drying stage assurance suitable between balance.

In addition, the air displacement unit can be designed to have the recycling unit, and this recycling unit comprises variable speed drive/motor and air door equipment, solidifies thereby the air of discharging 140 ℉ (60 ℃) or 160 ℉ (71 ℃) is used for the acceleration of baking oven.This unit makes airborne 80% recycling at the most, drains into atmosphere with 20% simultaneously.Such design is through provide energy efficiency as follows: the recycling warm air, thus need less energy to be used for heating unit.

In some embodiments, in order to help that sagging resistance is provided in wet environment, can change between the entering spraying and/or the temperature and humidity of the air of drying oven.It is desirable to through following controlling moisture: to getting between spraying or the air of baking oven heats, cooling, humidification or dehumidifying.Heating, cooling, humidification or the required degree that dehumidifies depend on that air is getting between spraying or temperature and humidity during baking oven.

On the one hand; Get into that air ratio between spraying is needed will be colder and comprise under the situation than needed still less moisture (promptly having lower relative humidity), the air that gets into through usual manner (for example utilizing gas, electricity or steam heating method) heating.Then, through vapour distributor or can moisture be introduced in the warm air by the atomizing/pressurized water of absorption of air.

On the one hand, air between spraying is more warm and have under the situation of higher relative humidity getting into, and with the air cooling that gets into to required air dew point, and heats through usual manner (for example utilizing gas, electricity or steam heating method) warm air.Then, through usual manner (for example through cold water coil or transpiration cooling) air is cooled off.This method has been removed moisture from system, and has reduced between spraying and/or the AT in the drying oven.

Can utilize other ordinary methods to come between dry spraying and/or warm air in the drying oven or damp atmosphere.For example; Can use the siccative dehumidification system, wherein, siccative is installed on the swiveling wheel; Along with this takes turns rotation; Siccative is the process air through getting into alternately, and at this moment moisture is adsorbed, then when dry this siccative through regeneration zone (gaslight of for example baking through direct fire or start to exchange fire roasting water/steam coil) and discharge moisture.This process is along with the rotation of desiccant wheel is carried out continuously.This desiccant system can comprise exsiccant siccative, liquid desicoant or its combination.

Compsn of the present invention can be used for forming the primer coating (or DTM coating) with wide region build.In the exemplary embodiment, primer coating have about 20 microns to about 200 micrometer ranges, preferably about 25 microns to about 150 micrometer ranges, more preferably about 40 microns to about 130 micrometer ranges, 50 microns build more preferably from about.In the exemplary embodiment, the DTM coating have about 25 microns to about 200 micrometer ranges, preferably about 40 microns to about 150 micrometer ranges, more preferably at about 60 microns builds to about 100 micrometer ranges.

Except first water-based paint compositions, coating system of the present invention comprises containing of second water-based paint compositions of extra composition optional also comprising at least.Notably, second water-based paint compositions provides the water base top coat that the following undercoat that is mixed with chlorinated resin is had the wild phase capacitive.Second water-based paint compositions comprises at least a combination that preferably contains acid functionality's's (or its salt and/or its ester) resin He one or more pigment, and these pigment accumulative totals exist with the significant quantity that further describes as follows.Be applicable to that the resin in second waterborne compositions can be acyclic, non-aromatics cyclic, branching, linear, aliphatic series or aromatics.Preferably, at least a portion in the pigment thing comprises sheet shape pigment.The ground that meets the requirements, be used in second water-based paint compositions at least a resin independently or with another feature (such as coalescing aid and/or heating) combination as film-forming resin.When these second water-based paint compositions were coated on the following finishing coat that is mixed with chlorinated resin, top coat showed less foaming, less peels off, extraordinary weather resistance and improved adhesivity.

Second water-based paint compositions can be a single phase soln, and wherein one or more compositions (comprising said second resin Composition at least) are dispersed in the aqueous carrier basically fully.Perhaps, coating composition can comprise two phases or more heterogeneous.Contain two mutually or more the heterogenetic compsn can be the dispersion-s form, such as wherein one mutually or heterogeneous dispersion-s in the external phase of another material and/or another phase.Some dispersion-ss are suspensoid forms, include but not limited to colloidal suspension.In some embodiments, coating composition is wherein to include emulsion or the latex that is dispersed in the polymer particles in the aqueous carrier.Some compsns can be water dilutable.

The acid functionality of resin (if existence) can directly be suspended on the polymer backbone, perhaps can be connected on the skeleton through suitable link group.Suitably acid functionality's instance comprises carboxylic acid, sulfonic acid, phosphoric acid, these combination or the like.Various gegenions can be with providing in those embodiments of acid groups with salt form therein.Cationic instance like this comprises Na ⁺, Li ⁺, NH ₄ ⁺, K ⁺, these combination or the like.In preferred embodiment, the acid functionality comprises-C (O) ONH ₄ ⁺Advantageously, when comprising these segmental coating compositions when dry, the exsiccant coating discharges ammonia, thereby in the exsiccant coating, stays-C (O) OH functionality.

In the exemplary embodiment, suitable multipolymer is derived by following reactant and is obtained, and said reactant comprises (a) at least a aromatic reactants that contains the free redical polymerization functionality of suspension; (b) at least a free redical polymerization reactant with acid functionality's (or its salt or its ester) of suspension; But (c) optional at least a other copolyreaction things with free redical polymerization functionality.Such reactant is monomer, oligopolymer and/or resin normally.

The instance of reactant (a) includes, but not limited to vinylbenzene, alpha-methyl styrene, t-butyl styrene, 1; 3-di isopropenylbenzene, 2,4,6-Three methyl Benzene ethene, 2; 4-dimethyl styrene, 2; 4-phenylbenzene-4-methyl-1-pentene, 2,5-dimethyl styrene, 2-vinyl naphthalene, 3-vinyl toluene, 4-benzyl oxygen-3-methoxy styrene, 9-vinyl anthracene, α, 2-dimethyl styrene, these combination or the like.These can be substituted or not be substituted.The illustrative embodiments of resin comprises, with respect to the total overall reaction thing that is used to form this resin of 100 weight parts, the reactant of about 10 to 70 weight parts (a).

The instance of reactant (b) comprises the acids of undersaturated or other free redical polymerizations.In some embodiments, by one or more carboxylic acid or its acid anhydrides reactant (b) is provided with one or more acid groups.Instance comprises (methyl) vinylformic acid, Sorbic Acid, maleic anhydride, toxilic acid, Ba Dousuan, methylene-succinic acid, styracin, Zoomeric acid, oleic acid, linolic acid, arachidonic acid, TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M., fumaric acid, these combination or the like.The illustrative embodiments of resin comprises, with respect to the total overall reaction thing that is used to form this resin of 100 weight parts, the reactant of about 2 to 20 weight parts (b).Preferably; The acid functionality is high singularly, because mix at least 3 weight % that one or more sour functional response's things in the resin are gross weights of the used total overall reaction thing of preparation resin, at least 4 weight %, at least 5 weight % and 10,15 or 20 weight % at the most.

The instance of reactant (c) comprises; But be not limited to; Vinyl ester, vinyl ethers, lactams such as N-vinyl-2-Pyrrolidone, (methyl) acrylic amide, N-substituted (methyl) acrylic amide, (methyl) Octyl acrylate, NP b-oxide (methyl) propenoate, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, 1, caprolactone (methyl) propenoate of 6-pinakon (methyl) propenoate, (methyl) IBOA, (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) propenoic acid beta-carboxyl ethyl ester, (methyl) Bing Xisuandingzhi, (methyl) NSC 20949, cycloaliphatic epoxides, α-epoxide, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinyl cyanide, maleic anhydride, methylene-succinic acid, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) n-butyl acrylate, (methyl) methyl acrylate, (methyl) NSC 11786, (methyl) vinylformic acid, N-caprolactam, (methyl) stearyl acrylate ester, hydroxy-functional, (methyl) vinylformic acid stearyl, (methyl) Isooctyl acrylate monomer, (methyl) Hydroxyethyl acrylate, (methyl) vinylformic acid hydroxyl methyl esters, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxyl isopropyl ester, (methyl) vinylformic acid hydroxy butyl ester, (methyl) vinylformic acid hydroxyl isobutylate, (methyl) vinylformic acid tetrahydro furfuryl ester, these combination or the like.The illustrative embodiments of resin comprises, with respect to the total overall reaction thing that is used to form this resin of 100 weight parts, the reactant of about 10 to 80 weight parts (c).

The resin that can be used in second waterborne compositions can utilize current various suitable polymerization technique known or following exploitation to form by constituting polymerization ofathe reactants.Patent Application No. 11/560,329 has further described these technology in (open 2007/0110981A1, on May 17th, 2010).

In some embodiments, second waterborne compositions is the latex composition form.This latex composition can comprise single-stage and/or multistage latex polymer.Preferred single-stage latex polymer can have at least-5 ℃, more preferably at least 15 ℃, most preferably at least 25 ℃, best at least 30 ℃ second-order transition temperature (Tg).The preferred single-stage latex polymer that uses have less than 75 ℃, be more preferably less than 65 ℃, most preferably less than 55 ℃ Tg.Tg can adopt DSC (DSC) technical measurement in practice of the present invention.

Preferred multistage latex polymer has 10 to 50wt% hard section and 50 to 90wt% soft section.Hard section preferably has about 35 to 70 ℃, 35 to 130 ℃ Tg more preferably from about, soft section Tg that preferably has between 0 to 30 ℃.

Also possibly advantageously use the gradient Tg latex polymer that utilizes the continually varying monomer to process.Resulting polymers has such DSC curve usually, and this DSC curve does not have the Tg flex point, and we can say to have the Tg ladder of unlimited number basically.For example, can begin, a bit begin the soft level of reinforced low Tg monomer composition in the hard level of high Tg monomer material at polymeric then by the monomer material of high Tg.The multistage latex polymer of gained will have gradient Tg from high to low.In another embodiment, possibly advantageously the hard level of high Tg monomer composition is fed in the soft level of the low Tg monomer composition.Gradient Tg polymkeric substance also can use with many Tg polymkeric substance.

Except free redical polymerization resin as herein described, the optional resin Composition that comprises one or more other kinds of second resin Composition.The instance of other resins comprises urethane, polymeric amide, polyimide, halogenated polymer, silicone, polyester, Synolac, polyolefine, (methyl) acrylics, these combination or the like.

Second water-based paint compositions preferably comprises the combination of at least a resin and one or more pigment, and these pigment accumulative totals exist with the significant quantity that further describes as follows.One or more pigment are added in second water-based paint compositions usually, to assist thickening combination and/or sagging resistance to be provided and to improve coating processes.These pigment can be organic and/or inorganic.Mineral dye is preferred.Pigment can have different shape, such as sheet shape, needle-like, ellipse, circle, sphere, irregularly shaped, these combination or the like.

Be not to be entangled in theory, the optimum filling amount of the top coat that pigment forms in by second water-based paint compositions is considered to and can useful performance and coating characteristic be provided for coating system.For example, second water-based paint compositions preferably comprises the pigment content of q.s, thereby gained coating and following primer coating have the consistency of improvement.Be not to be entangled in theory, the consistency of this improvement can prevent foaming and the adhesion loss between prime coat and the top coat.In addition, we believe, best pigment loading level can prevent entrapped air, moisture or gas, and entrapped air, moisture or gas otherwise will during applying to base material, produce bubble perhaps cause and bubbles or coating is peeled off from base material and/or prime coat.In many aspects, these performances are with to use the industry prejudice that advantage and predicted performance can descend along with the increase of pigment loading level opposite.

Some preferred embodiment in; Second water-based paint compositions comprises the pigment of significant quantity; It is inorganic pigment granules; The gained coating that the result is processed by this second coating composition comprises, based on the TV of dry coating, and about 15 to 85, preferred about 20 to 80, the particle of 25 to 80 volume percent more preferably from about.These granules of pigments are non-adhesive particles, they with coalescence basically and (for example sticker) one-tenth membrane granule of assisting to form a binder matrix part in the gained coating be different.Therefore, be meant that granules of pigments keeps at least a portion, preferably whole basically of their particle characteristics (independent or as coacervate or aggregate) about the term " non-sticker " of granules of pigments.Preferred pigment particle is non-adhesive particle, their film forming not basically under the condition that is used to form second water-based paint compositions.Particulate maybe be from the outstanding arbitrary portion of coatingsurface like this, and for the purpose of the pigment volume concentration (PVC) (PVC) of count particles in coating, those protuberances are considered to the part of pigment volume.Best pigment loading level in the topcoat compositions can provide useful performance and apply characteristic for coating system, has reduced the entrained air during applying and has improved the adhesivity of top coat and prime coat.

Preferably, the part of the pigment content in second water-based paint compositions comprises one or more sheet shape granules of pigments.Sheet shape particle has excellent thickening character, excellent sag-resistant property is provided, also helps air to discharge.

The instance of sheet shape pigment comprises one or more in following: clay such as china clay, mica, talcum, these combination or the like.Advantageously, it is littler that china clay and some other sheet shape particles compare the glossy influence, and this is useful when needing the top coat of higher gloss.

In some embodiments; Second water-based paint compositions preferably comprises; With respect to the gross weight of second water-based paint compositions of 100 weight parts, about 0 to 50 weight part, preferred about 10 weight parts, more preferably from about 15 to 50 weight parts, most preferably up to the sheet shape particle of about 35 weight parts.

Sheet shape particulate size (being expressed as volume averaging) can change in particle to the coarse grained wide region of fine size.In the exemplary embodiment, sheet shape particle can have in about 0.5 to 50 micron scope, in preferred about 1 to the 10 micron scope, the size in 3 to 5 microns the scope more preferably from about.On the one hand, preferably at least about 50wt%, more preferably at least about 75wt%, most preferably have the size in about 0.5 to 50 micron, preferred about 1 to 10 micrometer range at least about the sheet shape particle of 95wt%.

Advantageously, all pigment contents in second water-based paint compositions not all only are sheet shape particle form also.In itself, sheet shape particle can help thickening combination and can help to improve the anti-droop and the coating of coating composition.But excessive sheet content possibly form the obstruct to moisture in the dry coating and entrap gas.This possibly make and more be difficult to during making and/or being coated with, from coating, discharge entrapped air and/or entrapped moisture.Therefore, in some embodiments, the pigment in second water-based paint compositions comprises at least a non-sheet shape particle that uses with at least a shape particle combination ideally.

Various non-sheet shape particles can use with the combination of sheet shape particle.Instance comprises one or more insoluble vitriol; One or more insoluble carbide; One or more insoluble nitride; One or more insoluble oxynitrides; One or more insoluble oxycarbides; One or more insoluble oxide compounds; One or more insoluble carbonates; These combination or the like.These instance comprises; The vitriol of one or more among Be, Mg, Ca, Sr, Ba, Al, Ti, transition metal, lanthanide series metal, actinide metals, Si, Ge, Ga, Al, Sn, the Pb, carbide, nitride, oxide compound, oxynitride, oxycarbide and/or carbonate, these combination or the like.The particulate embodiment comprises BaSO like this ₄, titanium oxide, SiC, SiN, TiC, TiN, these combination or the like.In some preparations, BaSO ₄Be preferred.In some embodiments, some pigment help to keep gloss, help thickening second water-based paint compositions to allow air to overflow simultaneously, and help to provide for the gained coating perviousness of level of hope, and moisture passes in and out the gained coating well as a result.

Non-sheet shape particulate size (being expressed as volume averaging) can change in particle to the coarse grained wide region of fine size.In the exemplary embodiment, the non-sheet shape particle can have in about 0.1 micron to 50 microns scope, the size in preferred about 0.5 to the 10 micron scope.On the one hand, preferably at least about 50wt%, more preferably at least about 75wt%, most preferably have the size in about 0.1 to 50 micron, preferred about 0.5 to 10 micrometer range at least about the non-sheet shape particle of 95wt%.

The weight ratio of sheet shape pigment and non-sheet shape pigment can change in wide region.For example, an embodiment of second water-based paint compositions comprises, coating based solid gross weight, the circular relatively BaSO of about 14.5 weight % ₄The sheet shape china clay of particle and about 14.5 weight %.

Pigment also plays other effects in coating.As an example, pigment can be used as thickening material, be used for helping to reduce foaming and being used to help improve sagging resistance.In addition, it is described active one or more about optional extra composition as follows to play in coating, to add pigment.

In some embodiments, second water-based paint compositions preferably comprises, with respect to second resin Composition of about 100 weight parts, and at least 10 weight parts, more preferably at least 15 weight parts and 50 weight parts, the sheet shape particle of about at the most 35 weight parts most preferably at the most.

Extra particulate component in second water-based paint compositions can be the form of following one or more extra compositions.

The amount of second resin Composition in second water-based paint compositions can be selected in wide region.Generally speaking, if the amount of resin Composition is low excessively, possibly be difficult to film forming so, more be difficult to formation base material is had enough adhering film, this film possibly have insufficient erosion resistance or other performances, or the like.If it is excessive to use, possibly is difficult to the pigment preparation infill system so or more is difficult to process the material that can be coated on the base material.Weigh the advantages and disadvantages, second water-based paint compositions preferably comprises, based on the gross weight of water-based paint compositions, and about 10 to about 70 weight %, more preferably from about 15 to about 50 weight %, 20 to about 40 weight % said second resin Composition most preferably from about.

Second resin Composition mixes with the waterborne liquid supporting agent, and " water-based " in the aqueous carrier of wherein using in second water-based paint compositions is as above defined for the aqueous carrier of using in first water-based paint compositions.Except water, optional one or more the extra optional supporting agents altogether that comprises of the aqueous carrier of second water-based paint compositions.(comprise and assist film forming and/or paint vehicle to stablize) for various purposes, can use common supporting agent.Altogether the instance of supporting agent comprises, butyl cellulose, alcohols (such as butanols), coalescing agent (for example traditional ester alcohols, like Eastman Texanol product, and/or low VOC coalescing agent, like USP 6,762,230 is said), glycol ethers, these combination or the like.Desirably, the so-called common supporting agent that does not contain VOC is preferred.

The amount that is included in the common supporting agent in second water-based paint compositions can change in wide region.Consumption depends on various factors, comprise common supporting agent type, add supporting agent altogether purpose, possibly be used for second water-based paint compositions is coated to coating technique on the base material or the like.In the exemplary embodiment, second water-based paint compositions can comprise, and based on the common supporting agent and the gross weight of water that are included in the said composition, about 0.3 weight % is to the common supporting agent of about 20 weight %, preferred about 1 weight % to 5 weight %.

In order further to strengthen thermotolerance, can in second dispersion-s, mix one or more reagent of assisting reflecting heat and electromagnetic energy and/or opposing to absorb heat and electromagnetic energy.

The instance of reagent is included in the reagent of describing in U. S. application number 60/360,804 (with people's such as Turner name, the acting on behalf of case 160-P-2021USP1) of the common pending trial that the applicant submits on July 1st, 2010 like this.These reagent can mix in the coating according to current conventional practice known or following exploitation.

In some embodiments, such reflection or absorption reagent can comprise non-ir absorption colored pigment.Exemplary this pigment can be inorganic or organic in nature, and it includes but not limited at U.S. Patent number 6,454; 848B2 (people such as Sliwinski), 6,616,744B1 (people such as Sainz), 6; 989; 056B2 (Babler) and 7,157,112B2 (Haines) and in U.S. Patent Application Publication US 2005/0126441A1 (Skelhorn), relate to those.Mineral dye is special ideal; It comprises the single or blended MOX that is formed by various metals, and said metal for example is aluminium, antimony, bismuth, boron, chromium, cobalt, gallium, indium, iron, lanthanum, lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, silicon, tin, vanadium or zinc.Possibly hope to avoid utilizing the embodiment that contains Zn etc., if in the gained top coat, use such composition have degraded or otherwise with following prime coat in the trend of chlorinated resin reaction.As option, use can provide the blended metallic combination of stabilising effect as stated.For example, in the system that comprises barium/zinc, calcium/zinc, barium/calcium/combinations such as zinc, can obtain the hybrid metal stabilization

Exemplary MOX comprises Cr ₂O ₃, Al ₂O ₃, V ₂O ₃, Ga ₂O ₃, Fe ₂O ₃, Mn ₂O ₃, Ti ₂O ₃, In ₂O ₃, TiBO ₃, NiTiO ₃, MgTiO ₃, CoTiO ₃, ZnTiO ₃, FeTiO ₃, MnTiO ₃, CrBO ₃, NiCrO ₃, FeBO ₃, FeMoO ₃, FeSn (BO ₃) ₂, BiFeO ₃, AlBO ₃, Mg ₃Al ₂Si ₃O ₁₂, NdAlO ₃, LaAlO ₃, MnSnO ₃, LiNbO ₃, LaCoO ₃, MgSiO ₃, ZnSiO ₃, Mn (Sb, Fe) O ₃And composition thereof.Said MOX can have above-mentioned U.S. Patent number 6; 454; Rutile-cassiterite described in the 848B2 (kassiterite), spinel and/or corundum-hematite crystals crystalline network; Perhaps can be the main body component with corundum-rhombohedral iron ore crystalline texture, it comprises one or more elements as the object component, and said element is selected from aluminium, antimony, bismuth, boron, chromium, cobalt, gallium, indium, iron, lanthanum, lithium, magnesium, manganese, molybdenum, neodymium, nickel, niobium, silicon, tin, vanadium and zinc.

Because traditional carbon black pigment has the high IR absorptivity and the carbon black pigment that in traditional dark paint vehicle and colorant, is widely used, so the non-ir absorption pigment of black is noticeable especially.The non-ir absorption pigment of various black is commercially available, and it comprises, such as by Ferro Corporation with COOL COLORS ^TMAnd ECLIPSE ^TMThose blended metal oxide pigments of trade mark supply, for example V-778 COOL COLORS IR Black, V-780 COOL COLORS IR Black, V-799 COOL COLORS IR Black, 10201 ECLIPSE Black, 10202 ECLIPSE Black and 10203 ECLIPSE Black; Such as by Shepherd Color Company with ARTIC ^TMThose blended metal oxide pigments of trade mark supply, for example ARTIC Black 376, ARTIC Black 10C909, ARTIC Black 411 and ARTIC Black30C940; Such as those blended metal oxide pigments of supplying with number 42-707A and 707V10 by Tomatec America Inc.; With by BASF Corp. with PALIOGEN ^TMNa Xie perylene base or other organic colorants of trade mark supply comprise PALIOGEN Black S 0084.

These suppliers also provide the non-ir absorption colored pigment with the various colors that are different from black with identical trade mark usually, and these can be used in the disclosed coating composition equally.Exemplary non-ir absorption non-black pigment comprises mineral dye, such as red stone, Magnesium Silicate q-agent, lime carbonate, aluminosilicate, silica and various clay; Pigment dyestuff comprises plastic pigments, such as solid bead pigment (for example polystyrene bead or SE pearl); With the microballoon pigment that contains one or more spaces (those that for example discuss among U.S. Patent Application Publication US 2007/0043162A1 people such as () Bardman).

Other exemplary non-ir absorption pigment comprise EXPANCEL ^TM551DE20 vinyl cyanide/vinylchlorid expanded beads (from Expancel Inc.), SIL-CEL ^TM43 glass microfiber fillers (from Silbrico Corporation), FILLITE ^TM100 ceramic spherical particles (from Trelleborg Fillite Inc.), SPHERICEL ^TMHollow glass ball (from Potter Industries Inc.), comprise the 3M ceramic microsphere (from 3M) of G-200, G-400, G-600, G-800, W-210, W-410 and W-610; The 3M hollow microsphere (also from 3M), the INHANCE that comprise 3M performance additive iM30K ^TMUH 1900 polyethylene particles (from Fluoro-Seal Inc) and BIPHOR phosphagel phosphaljel are (from Bunge Fertilizantes S.A., Brazil).

Disclosed coating composition can also comprise the pigment that non-ir absorption does not have color, such as titanium oxide and white zinc oxide, if any one in them will provide white but not colored coating composition not having under the situation of colored pigment to use.So no coloured pigment is added to can provide in the colored pigment of above-mentioned non-ir absorption and have tone (lightened shade) that brightens and colored paint vehicle and the colorant that improves opacifying power (hiding power).Preferably, disclosed coating composition comprises, based on all solids, and about 8 to about 50wt%, 20 to about 30wt% pigment more preferably from about.Represent that based on pigment volume concentration (PVC) disclosed coating composition preferably comprises about 10 to about pigment of 40%, more preferably from about 15 to about 20%.The said composition ideal does not contain or is substantially free of the ir absorption colored pigment, for example carbon black, black iron oxide, oxidation palm fibre and give birth to brown.

If desired, optional being comprised in second water-based paint compositions of various other supplementary components.These instance comprises one or more froth breaking auxiliary agents, grinding aid, wetting agent, tensio-active agent, coalescing aid, processing aid, slipproofing agent, anti-wear agent, conductivity reagent, static inhibitor, tinting material, anticorrosive auxiliary agent, thickening material, sag-resistant reagent, softening agent, inhibitor, UV stabilizer, biocide, mycocide, filler, these combination or the like.These can use according to current conventional practice known or future development.

Can utilize various technology preparation second water-based paint compositions.Exemplary techniques is said in an embodiment hereinafter.

Topcoat compositions of the present invention can be used for forming the top coat with wide region thickness.In the exemplary embodiment, top coat have about 15 microns to about 200 micrometer ranges, preferably about 15 microns to about 100 micrometer ranges, more preferably at about 30 microns thickness to about 50 micrometer ranges.

Coating composition of the present invention and coating system can be used for being coated with various base materials.Exemplary substrate comprises natural and engineering construction material, freight container, flooring material, body of wall, furniture, other material of construction, Motor vehicles member, aircraft component, truck, railcar and mover, marine member, mechanical component, veneer sheet, element of installation, utensil, packing or the like.Exemplary substrate material comprises metal, metal alloy, intermetallic compsn, containing metal mixture, these combination or the like.Illustrative metal comprises aluminium, steel, weathering steel, stainless steel or the like.Coating composition can be coated on the new base material, perhaps can be used for rebuilding old base material.

During use, base material to be coated with is provided.This base material can be perhaps can at least partly being coated with by previous coating system (such as the so-called shop primer that is used for the coating metal base material) of exposing.Exemplary shop primer comprise traditional shop primer and the U.S. Patent Application Serial Number 61/322,795 (" Waterborne Shop Primer ", people such as Prevost) submitted on April 9th, 2010 the applicant in disclosed novel priming paint.Thereby cleaned base material is removed grease, dirt and other pollutents and possibly hoped.Can remove also and can not remove the coating that is pre-existing in, this depends on particular case.When base material all set, first water-based paint compositions is coated at least a portion of substrate surface.Alternatively, allow the dry or part drying of coating, thereby form undercoat.If desired, can apply the coating of one or more layers extra said first water-based paint compositions.Usually, single coating is suitable.Then, second water-based paint compositions is coated at least a portion of undercoat, and the dry top coat that forms.If desired, the extra section that does not have undercoat of base material also can be coated with by top coat.If desired, can apply the coating of one or more layers extra said second water-based paint compositions.Usually, single coating is suitable.Can utilize any proper technology known in the art, such as be coated with through brushing, spraying, spin coating, roller coat, curtain, dip-coating, concave surface coating or the like, first and second dispersion-ss are coated on the base material.

On being coated in the primer coating that is formed by first waterborne compositions, the quilt that topcoat compositions can also be coated in other types is not coated with being coated with and forms coating on the base material.For example, some embodiments of second water-based paint compositions can also be used for the top and are coated with and or be not coated with stainless steel and/or epoxy primer coating (submit simultaneously like the applicant's application therewith, autograph for described in the common co-pending application of " WATER-BASED COATING SYSTEM WITH IMPROVED ADHESION TO A WIDE RANGE OF COATED AND UNCOATED SUB STRATES INCLUDING MUFFLER GLADE STAINLESS STEEL ").

Coating system of the present invention is particularly suitable on freight container, forming supercoat.Preferably, this coating system is used to the freight container that relates in the through freight transportation.Many international standards that are applicable to through at least a freight freight container in the following system that meet at least basically in such freight container, said system are the carriage of goods by sea system of water route shipping goods, the system of transportation by railroad goods and/or the system of transport by road goods.Such freight container is under its length of life is exposed to like extreme environments such as weathering, salt solution exposure, fresh water exposure, Exposures to Sunlight usually.Even such freight container is made by corrosion resistant material (such as stainless steel and/or weathering steel) usually, but still need further resistance to wear, protection such as anticorrosive and/or decorate.

Exemplary through freight freight container is commonly called dry freight container in industry.These freight containers generally include the metal frame that limits the freight container border.Wall, floor and smallpox panel are connected on this framework through bolt, welding, rivet etc.Panel can be processed by various metals, metal alloy, intermetallic compsn or above-mentioned other metal-containing material.Weathering steel (being called as COR-TEN board steel sometimes) is because its low cost and erosion resistance are generally used for preparing panel.The surface of weathering steel with the similar mode oxidation of aluminium, but this oxidation form to intercept to protect following steel to avoid further corrosion.According to the ASTM standard, can obtain comprising the weathering steel of A242, A588 and A602 grade.Container framework also can be processed by weathering steel or different metal compsn.Although weathering steel development erosion-resisting protectiveness oxidation is intercepted, industry still often applies protective coating widely on by the intermodal container of weathering steel manufacturing.This coating also can provide decoration, brand identity, barcode and other marks.

The present invention is when being used to protect intermodal container to show excellent adhesivity and performance when (comprising those that made by weathering steel).The typical set vanning that will provide has one deck oxide compound at least a portion on surface.In some cases, also so-called shop primer is coated on some surfaces, but often is not coated on the weld seam.Shop primer is rich Zn priming paint, and it helps in freight container assembly process protection steel protect it from corrosion.

The two does not all demonstrate excellent adhesivity to first water-based paint compositions of the present invention to being coated with metallic surface shop primer and that scribble shop primer.Therefore, needn't remove shop primer on the weathering steel.Yet,, be ideal from the surface removal oxide compound for better adhesivity.This for example sand-blast completion in any appropriate manner.In case cleaned the surface, just can form undercoat of the present invention.After this, on undercoat, form top coat of the present invention.Although the two all is water base for undercoat and top coat, the gained coating system provides excellent gloss, weather resistance, erosion resistance, adhesivity, anti-whipability, anti-separability and resistance to cracking.

Embodiment

Now, with reference to following exemplary embodiment the present invention is described.

Embodiment 1A

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With mixture at the mesh-of-grind that is dispersed at a high speed down 5-6Hegman, then with mixture discharge like following table 1b.In some embodiments, hope Bentone LT material is pre-dispersed in a part of water.

The composition of in above-mentioned, listing among the interpolation table 1c.

Sample 1 and 2 priming paint are formulated into the situation that is used for experiencing high use temperature.The priming paint of sample 1 further is mixed with has low pH, the anti-sudden strain of a muscle rust property that is used to improve.The priming paint of sample 3 has epoxy component, also is used to improve thermotolerance.

Embodiment 1B

Abide by embodiment 1A, the process of sample 3, difference are that Epi-rez 3510 epoxy resin add with each composition of table 1c rather than with each composition of showing 1a.

Embodiment 2

Water-based top coat preparation

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With mixture at the mesh-of-grind that is dispersed at a high speed down 6.5Hegman, then with mixture discharge like following table 2b.

The top coat of sample 1 has high relatively pigment to sticker ratio, and is brown.The top coat of sample 2 has high relatively pigment to sticker ratio, and is white.

Embodiment 3

Water-based primer with Zn

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With mixture at the mesh-of-grind that is dispersed at a high speed down 5-6Hegman, then with mixture discharge like following table C1b.Bentone LT can be pre-dispersed in a part of water.

Embodiment 4

Water base top coat

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With mixture at the mesh-of-grind that is dispersed at a high speed down 6.5Hegman, then with mixture discharge like following table C2b.

Embodiment 5

Performance test

The coating for preparing among the above embodiment is applied on the standard dry freight container line with the bottom line correction; And when moving with similar LV when being used with suitable curing oven ((System and Method for Drying Five-sided Container (Nowack)) is said such as the U.S. Patent Application Serial Number of submitting on July 16th, 2,010 12/837,833).Embodiments of the invention have passed through IICL regulation and industry standard performance test.In order to obtain better result, make first waterborne compositions dry basically before second waterborne compositions applies.

The performance test of priming paint/top coating system is reported in the following table.

According to ASTM D-714 observation foaming grade.

Test set: Illonis Instruments model 7001.

Testing method

Utilize the sagging resistance of the water based primer compositions of test of dry method sagging resistance and wet method sagging resistance test evaluation embodiment 5-8.

The test of dry method sagging resistance-this test is carried out in exsiccant typical case " drying " environment in coating therein.

1. in container, prepare sample through fully stirring with spatula.

2. filter if desired to remove macrobead or skinning.

3. with the temperature regulation to 21 of sample ℃ ± 2 ℃.

4. suitable test card card is attached on the spreading blade (drawdown plate).For example, use black and white Leneta card according to the color of testing sample.

5. go up in position, straight flange is fixed on the spreading blade.

6. place anti-sagging scraper (1-6 Mill (25-152 micron) scraper or 3-12 Mill (635-305 micron) scraper) at the far-end of card, wherein open side is towards the operator.

7. if desired, with collect paper place just the card lower edge below.

8. stir paint vehicle that the back at once will about 8ml and place the front of drawdown rod.

9. with the uniform acceleration Spreed coated paint of about 6 feet per seconds (15.24cm/ second), wherein, make spreader press straight flange, to keep straight path.

10. immediately with vertical mode suspension card, wherein the blade coating band is in horizontal direction just as the crosspiece of upright ladder, and the thinnest blade coating band is at the top.

11. make sagging card dry with such position.

12. after the film drying, note breach interval, and correspondingly discern respective strap in anti-sagging appearance marked.

13. observe sagging pattern, ignore the bottom band, this band is the position reference of the band of conduct on it only.

14. select can not cross over minimum (the thickest) band of the next lower band of contact at interval.It is called as index band (index stripe).

15. estimate the degree of the bar tape merge of next low band (band after the index) below it.

15.1 the merging degree of band after the index

16. multiply by the interval steps between the band after index band and the index with the mark of step 15.1, thereby obtain " index attaches benefit ".

17. sagging resistance is reported as the index band attaches benefit at interval with index summation.This numerical value is called as the anti-sagging index of level of coating.

18. with Mill or the anti-sagging index of micron report (usually with the Mill report).

(statement: in each table of embodiment 5-8, this is reported as " sagging indoor conditions ").

The test of wet method sagging resistance-this test is carried out in representative " humidity " environment of exsiccant at coating therein.

This test with " test of dry method sagging resistance " similarly mode carry out, difference is described below.

For step 6, use the anti-sagging scraper of 3-12 Mill (76-305 micron) or 12-60 Mill (305-1524 micron) Leneta.

For step 10, process scrape film after, immediately with its be suspended on the bottom have three inches (7.6cm) water 5 gallons (20 liters) bucket in.The mode that is horizontal with the paint vehicle band hangs to scrape films, wherein less Mill thickness at the top.Cover lid on bucket, and made sample drying 20 minutes.The relative humidity of this test chamber is estimated as approximately and surpasses 80%.

For assess sample, thus enough sagging cross the following next one more the paint vehicle band in the paste paint material band should be considered to Mill (micron) thickness that occurs failing.In addition, record paint vehicle band forms the position of dripping tear.This is the single failure go-to field on a paint vehicle.In each table of embodiment 5-8, this is registered as " sagging wet condition ".

Embodiment 6

Water based primer compositions with polyurethane thickener of different amounts

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With mixture disperseing at a high speed down and being milled to the Hegman specification of 5-6NS, then with mixture discharge like following table 6b through moderate.

The composition of in above, listing among the interpolation table 6c.

Embodiment 7

Aerosil with different amounts resists sagging dose water based primer compositions

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

Attention: the HSD among the table 7a representes " high speed dispersion device "

With mixture disperseing at a high speed down and being milled to the Hegman specification of 5-6NS, then with mixture discharge like following table 7b through moderate.

The composition of in above, listing among the interpolation table 7c.

Embodiment 7 shows that aerosil does not help the sagging resistance in wet environment.

Embodiment 8

Water based primer compositions with CAS agent of different amounts

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

With the mixture of sample 1 and 2 in the Hegman specification that is dispersed to 5-6NS at a high speed down, and with the mixture of sample 3 and 4 through the medium 5-6NS Hegman that is milled to, usefulness is like the mixture discharge of following table 8b then.

The composition of in above, listing among the interpolation table 8c.

Before test was sagging, all samples all added 5% water.

Embodiment 8 shows that Bentone LT provides desirable sagging resistance in wet environment, and without any need for extra anti-sagging dose or thickening material.

Embodiment 9

Water based primer compositions with CAS agent of different amounts

Following composition is added in the mixed at high speed container.Only if statement is arranged in addition, all list consumption all is weight part.

The mixture of sample 1 and 2 is dispersed to 5-6NS Hegman under at a high speed, discharges with mixture then like following table 9b.

The composition of in above, listing among the interpolation table 9c.

Consider this specification sheets perhaps from the disclosed practice of the present invention of this paper, other embodiments of the present invention are tangible to those skilled in the art.Those skilled in the art can carry out various omissions, modification and variation to principle as herein described and embodiment under the prerequisite that does not break away from desired true scope of the present invention of claims and spirit.

Claims (25)

1. water-based paint compositions, it comprises:

A. aqueous carrier;

B. with said aqueous carrier blended resin Composition; Alternatively

C. one or more are dispersed in the CAS agent in the said water-based paint compositions, and wherein, said one or more CAS agent comprise hydrophilic clay, and exist with the amount that is higher than 1 pound per 100 gallons (the every 100L of 0.12kg) said water-based paint compositions.

2. water-based paint compositions, it comprises:

A. aqueous carrier;

B. with said aqueous carrier blended resin Composition; With

C. one or more are dispersed in the CAS agent in the said water-based paint compositions; Wherein, Said one or more CAS agent comprise hydrophilic clay; And exist with q.s, thereby make at least 60% of sagging resistance that the sagging resistance of said water-based paint compositions under 80% relative humidity and 25 ℃ is said water-based paint compositions under 50% relative humidity and 25 ℃.

3. like the water-based paint compositions of any aforementioned claim, wherein, said one or more CAS agent comprise by organically-modified clay.

4. like the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions has the pH less than 6.

5. as the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions comprises, and the comprising by said one or more CAS agent of organically-modified clay of per 10 weight parts is less than anti-sagging dose of the association type of 2 weight parts.

6. like the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions is substantially free of anti-sagging dose of association type.

7. like the water-based paint compositions of any aforementioned claim, wherein, said one or more CAS agent comprise bentonite.

8. like the water-based paint compositions of any aforementioned claim, wherein, said one or more CAS agent have the average particulate size less than 1 micron.

9. like the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions has the 50 Stormer viscosity to 90Krebs unit under 25 ℃.

10. like the water-based paint compositions of any aforementioned claim, wherein, said resin Composition comprises at least a chlorinated resin.

11. like the water-based paint compositions of claim 10, wherein, said at least a chlorinated resin comprises polyvinylidene chloride.

12. like the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions also comprises one or more fillers, said filler is selected from by BaSO ₄, CaCO ₃, the group formed of rhombspar, wollastonite, silica, chlorite, talcum, china clay, mica, granulated glass sphere and composition thereof.

13. like the water-based paint compositions of any aforementioned claim, wherein, said water-based paint compositions comprises the filler that one or more its total oil number is about 10 to 40g every 100g filler gross weights.

14. a coating system, it comprises:

A. first water-based paint compositions, it comprises the water-based paint compositions of any aforementioned claim; With

B. second water-based paint compositions, it comprises:

I. second aqueous carrier; With

Ii. with the said second aqueous carrier blended, second resin Composition.

15. a quilt is coated with goods, it comprises:

Substrate surface;

Directly or first coating that at least a portion of said substrate surface, forms indirectly, said first coating comprises the coating system of any aforementioned claim; Alternatively,

Directly or second coating that at least a portion of said first coating, forms indirectly.

16. the method for the metallic surface of a coated article, said method comprises the steps:

Any described water-based paint compositions in the claim 1 to 14 is coated at least a portion of the base material with metallic surface under the condition that effectively forms coating.

17. like the method for claim 16, wherein, said condition comprises, when said compsn has the pH in about 4 to 9 scopes, makes said composition dries.

18. like the method for claim 16 or 17, wherein, said water-based paint compositions forms the dry film of thickness in 25 to 130 micrometer ranges.

19. like method any among the claim 16-18; Wherein, Said condition comprise make in the environment of said compsn in relative humidity is being up to the scope of about 95% humidity dry, and the time period inner drying of said compsn in 10 to 30 minutes scopes.

20. like method any among the claim 16-19, wherein, said coating step comprises, said water-based paint compositions is sprayed at least a portion of said base material.

21. a method that is coated with freight container, it comprises the steps:

Freight container or its one or more members are provided;

Any described water-based paint compositions in the claim 1 to 14 is coated at least a portion on surface of said freight container or its one or more members.

22. a method that is coated with freight container, it comprises the steps:

Freight container or its one or more members are provided;

On at least a portion on the surface that is coated to said freight container or its one or more members under the processing condition that are modified to controlling moisture and temperature, said water-based paint compositions comprises with water-based paint compositions:

Aqueous carrier; With

With said aqueous carrier blended resin Composition.

23. a coating system, it comprises:

A. water-based paint compositions, said water-based paint compositions comprises

I. aqueous carrier;

Ii. with said aqueous carrier blended resin Composition; With

Iii. one or more are dispersed in the CAS agent in the said water-based paint compositions, and wherein, said one or more CAS agent exist with the amount that is higher than the said water-based paint compositions of the every 100L of 0.12kg; With

B. be coated to the film of said water-based paint compositions on the base material and make the exsiccant explanation in environment of said film with at least 75% relative humidity.

24. a coating system, it comprises

A. water-based paint compositions, said water-based paint compositions comprises

I. aqueous carrier;

Ii. with said aqueous carrier blended resin Composition; With

Iii. one or more are dispersed in the CAS agent in the said water-based paint compositions; Wherein, Said one or more CAS agent exist with q.s, thereby make at least 60% of sagging resistance that the sagging resistance of said water-based paint compositions under 80% relative humidity and 25 ℃ is said water-based paint compositions under 50% relative humidity and 25 ℃; With

B. be coated to the film of said water-based paint compositions on the base material and make the exsiccant explanation in environment of said film with at least 75% relative humidity.

25. one kind makes the water-based paint compositions of any aforementioned claim and/or the method for the coating system marketization; It comprises the step that following information is provided: said compsn and/or system can be used to the film of said water-based paint compositions is coated on the base material, and make said film dry in the environment with at least 75% relative humidity.